Treatment of hydrogenated rosin and product obtained



Sept. 14, 1943.

TREATMENT 0F HYDROGENATED ROSINAND PRODUCT OBTAINED Filed Deo. 15, 1942 R. F. B. COX

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1N VEN TOR.

BY M-A @wh-n2.

Trojan/EY Patented Sept. 14, 1943 UNITED slirlas' Milani- OFFICE:

' TREATMENT 0F HYDBOGENATED BOBIN- AND PRODUCT OBTAINED Richard F. B. Cox, Wilmington, Del., assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware Application December 15, 1942, Serial No. 469,089

(Cl. 26o-100) 18 Claims.

This invention relates to a process for the separation and recovery of resin acids from rosin and modiiied rosins.

Particularly it relates to a process for the recovery of a non-crystalline resulting rosin has a pronounced tendency to crystallize. Crystallization of the acids or the sodium acid abietate produces a crystalline rosin. Extraction of the acids by alkalies involves the subsequent acidification of the soap formed in order to free the rosin acids which is inconvenient and expensive, Moreover, these prior processes selectively remove abietic acid and abieticlike acids, and do not remove the rosin acids in the proportions in which they are present in the original rosin.

Rosin which is substantially freed of neutral bodies by following the present invention is adapted to many uses for which ordinary rosin, because of its lower melting point or its odor, is unsatisfactory.

The neutral bodies which can be removed from rosin (say ordinary refined wood rosin) by applying the principles of the present invention usually amount to about 10% by weight of the rosin. 'I'hey are soft and iiuid and have a marked eiect in lowering the melting point of the rosin, For example, a wood rosin which had a drop melting point of 80.5 C. before removal of the neutral bodies, melted at 88.7 C. after their removal by the process of the present invention. Likewise a gum rosin melted at 86.2 C. `before removing the neutral bodies, and at 91.2 C. afterwards. This increased melting pointis also carried over to` the esters such as.

the polyhydric alcohol esters such as ester gum prepared from the treated rosin.

This invention has as its object to provide anv improved process for the recovery of resin acids from rosin and modified roslns.

A further object is to ,provide an improved process for the production of rosin and modified rosins ofsubstantially increased melting point.

Another object is toA provide new products.

Other o bjects will appear hereinafter.

These objects are accomplished by the present invention by extracting the rosin or modified resin with an alkali salt of a weak inorganic u acid, and recovering the resin acids from the extract. For example, a solution of the rosin or modiiied rosin in an organic solvent may be extracted with a solution of an alkali sait of a weak inorganic acid in a suitable solventsuch as water which is capable of immiscibility with the organicsolvent, whereupon the resin acids are subsequently extracted from the alkaline salt solution by an organic solvent which is likewise capable of immiscibility with the alkaline salt solution. 'I'he resin acids taken up by this last solvent -are then recovered by evaporation ofthe organic solvent.

As the raw material I may employ any type of rosin such as wood rosin, gum rosin, so-callednon-crystallizing gum rosin, heat treated rosin, isomerized rosin, etc. Instead oi gum rosin, I may use a solution thereof, in turpentine such as the naturally occurring crude or rened pine oleoresin, or the non-crystallizing pine oleoresin of Palkln 2,176,660, etc. `I prefer to use a reilned rosin, that is a rosin which contains only a very small amount (2% or less) of gasolineinsoluble resin acids. The production of such a reiined rosin may be by any of the well-known refining processes such as with furfural or other selective solvent, selective adsorbents, etc, Instead of using rosin, I may use chemically modifled rosin such as disproportionated rosin which is known as I-B'ex" rosin and which is rosin which has been heated with a hydrogenating catalyst, but in the absence of hydrogen (U. S. patent to Littmann 2,154,629), polymerized rosin,

, hydrogenated rosin, etc.

As the solvent for the rosin or modied rosin -I prefer to use a lower aliphatic ether, that is,

an ether in which the number of carbon atoms in the alkyl groups ris not greater than six, and which is immiscible with water at ordinary temperatures I have found diethyl ether to be particularly satisfactory. Examples of other suitable ethers are di-isopropyl ether, di n-propyl ether, dibutyl ether, methyl propyl ether, methyl butyl ether, ethyl propyl ether, ethyl butyl ether, b-b-dichloroethyl ether, etc.

Instead of using a lower aliphatic ether as the solvent for the rosin or modiiled rosin, I may use other solvents such as liquid aromatic hydrocarbons such. as benzene, toluene, xylene, coal tar naphtha, etc.. petroleum hydrocarbon solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum 'naphtha, gasoline, kerosene. V. M. 8: P. naphtha, cyclohexane, tetrahydronaphthalene, decahydronaphthalene. di-

pentene, turpentine, chlorinated hydrocarbons such as chloroform, carbon tetrachloride, ethylene Adichloride, trichloroethylene, monochlorobenzene, etc.- I prefer to use a solvent which is immiscible with or capable of immiscdbility with water thus enabling the use of water as the solvent for the extracting salt. I prefer to use an ether solvent which is not substantially completely insoluble in water but which is not soluble in water to an extent greater than about 8% by weight such as diethyl ether,

The concentration of the initial solution may vary widely for example from about 10% to about 70% by weight of the rosin or modified rosin based on the weight of the solution.

As the extracting agent, I prefer to use ordinary borax, or sodium tetraborate with varying amounts of, or no, water of crystallization. Instead of sodium tetraborate, I may use sodium metaborate or other alkali metal salts of boric acids. Thus, I may use mixtures of alkali hydroxide and ordinary boric acid in varying'proportions. I prefer to use an extractant containing alkali in amount equal to one-half of the molar amount of boric acid. Thus, I prefer to AYuse sodium tetraborate (which is derived from 2 mols of sodium hydroxide and 4 mols of boric acid) or a mixture of sodium hydroxide and boric acid in the ratio of two mols of sodium hydroxide to four mols of boric acid.

'Ihe use of alkali metaborates results in extraction of a higher percentage of the neutral bodies than when alkali metal tetraborates such as borax, or alkali salts of other weak inorganic acids are employed.

Instead of an alkali salt of a boric acid, I may use strong or fixed alkali salts of other weak inorganic acids, such as carbonio acid, sulfurous acid, phosphoric acid. phosphorous acid, etc., provided that the salt when dissolved in water to form a solution has a pH between about 8.0 and about 12. In the case of the polybasic inorganic acids, I may use either the neutral or the acid salts provided that the pH of an aqueous 5% solution thereof is between 8.0 and! 45 12.0. Thus, I may use the alkali (sodium, potassium, lithium) carbonates, phosphates, sultes, and phosphites, or such acid salts as the alkali bicarbonates, and the di-alkali monohydrogen phosphates, etc. The acid, of which the alkali salt is employed, should be readily soluble in water or other solvent employed for the alkali salt, but substantially insoluble in the organic solvent used to dissolve the rosin or modiiied rosin initially and also in the organic extraction solvent used to extract the aqueous salt extract. I flnd it desirable to use those alkali salts which are readily soluble in water or other solvent for the alkali salt but which are substantially insoluble in the organic solvent used to dissolve the rosin or modified rosin initially, or to extract the aqueous salt extract.

The extractant is preferabhr employed .in solution in a solvent which is capable of immiscibility with the solvent employed in forming the rosin or modified rosin solution and which is a solvent for the extractant and is a non-solvent for rosin, modiiied rosin or the resin acids present therein. I prefer to use water as the solvent for the alkali salt extractant.

The concentration of the alkali salt solution may vary between wide limits provided that the pH of the solution falls between about 8.0 and about 12.0. Ordinarily, it will be preferred to weight of the alkali salt and the limit of solubility thereof at the temperature employed but preferably-not exceeding 10%. Usually a concentration of from about 1% to about 5% of the alkali salt will be employed. The percentages given refer to the anhydrous alkali salt. In the case of borax, I prefer to use an aqueous solution containing about 5% of the hydrous borax, i. e., the decahydrate. Y

The amount of the extracting agent employed may vary within wide limits depending upon the extent of completeness of removal of resin acids desired. In general, it may vary from about one-fifty to about iifty parts of the extracting agent to one part of the rosin or modified rosin.

Following the initial extraction with the aqueous alkali salt solution the aqueous extract phase containing dissolved or combined resin acids is separated from the rosin or modied rosin solution phase, and extracted with a solvent for the resin acids contained therein. The solvent used in this nal extraction should be capable of immiscibility with the alkali salt solution and may or may not be the same as that employed to initially dissolve the rosin or modified rosin. Any of the solvents enumerated above may be employed. Again, I prefer to use a lower aliphatic ether, specifically diethyl ether.

The amount of solvent employed in the final extraction may vary within wide limits depending upon its solvent power for resin acids and upon the quantity of resin acids present in the alkali salt solution extract. vary between about 5 and about 15 times the weight of extractant (alkali salt) present in the extract.

Following the final extraction with organic solvent the phases are separated in any suitable manner. The solvent phase is evaporated to recover the resin acids dissolved therein. The alkali salt phase may be employed in a re-extraction of the railinate phase obtained from the rst extraction. The alkali salt phase may be used over and over in a repetition of the extraction, until it becomes saturated with certain resin acids which are diflicultly or not at all removable by extraction with the organic solvent such as ether.

In the drawing, there is portrayed a flow sheet of the process as applied to hydrogenated rosin, using aqueous borax as the initial extractant and using ether as the solvent both initially for the hydrogenated rosin and for the final extraction. I'he hydrogenated rosin solution in ether and the borax solution are commingledin the initial extraction step (block 3), and the phases separated. The extract (block 5) is extracted (block 7) with fresh ether. The extract from this nal extraction (block 9) is evaporated to recover the hydrogenated rosin of high melting point (block 12) and ether (block 11) which is re-cycled. 'I'he rafiinate (block 8) is used to extract the ramnate (block 4) from the rst initial extraction. 'I'he extract from the second initial extraction (block 13) is extracted (block 14) with ether as before. The raffinate from the second iinal extraction (block 14) is again used to extract the railinate from the second initial extraction, etc. until the borax solution exerts no extracting power whereupon the hydrogenated resin acids therein may be precipitated therefrom if desired by neutralization with inorganic acid, and a fresh borax solution employed for employ a concentration between-about 0.5% by subsequent extractions. The ultimate residue is In general, it may assasic.

'rich in neutral bodiesderived from the hydrogenated rosin. a

If desired, fresh lots of borax solutlon'may be used instead of the vramnates from the nal extractions for the re-extraction of the ramnates from the initial extractions.

The extraction may be. conducted either batchwiseor continuously.' Where a continuous process is used, a solution of the rosin or modified rosin in diethyl ether may be contacted continuously either countercurrently or concurrently with the aqueous borax solution in a suitable packed tower, the aqueous extract being then passed into another tower where it continuously contacts fresh ether. 'Ihe result-l ing ether extract is then evaporated to recover the extracted rosin acids and the aqueous borax raffinate is recycled back to the first tower.

The mechanism of the process probably involves the following equation:

where AbOH' is a resin acid, RX is a strong alkali salt of a weakk acid, AbOR is an alkali salt of a resin acid and HX is a weak inorganic acid soluble in water but insoluble in the organic extraction solvent. When the rosin solution is contacted with the RX solution, the equilibrium is shifted to the right so that AbOR is formed to some extent and HX is formed in solution.v

When the aqueous solutionis separated and contacted with fresh solvent, the resin acid is taken up by the organic solvent so that the equilibrium is shifted back to the left. In this manner, the solution of alkali salt is substantially freed of resin acid and can be used over and over. In practice, however, some rosins and modified rosins such as for example unreiined or FF wood rosin contain small lamounts of socalled strong acids which combine with the RX solution and are not completely or are not at all extracted by fresh organic solvent. This difficulty is overcome by using a fresh RX solution after thel first several extractions. The fresh RX solution can be used over and over after the so-called strong -acids have been re-y moved by the first fewv extractions. The RX solution thus acts as a carrier for the resin acids, carrying them from a vsolvent containing a high concentration of vresin acids to a solvent containing little or no resin acid. The process of the present invention then is one in which there is no or only very. little consumption of chemicals.

The process of the present invention has an additional advantage over other processes for vsegregating resin acids in that the acids 'isolated comprise a mixture which is essentially non-crystalline and non-crystallizing. A further advantage is that the alkali solution carrier can be used over and over. A still further advantageis that no or only minor amounts of mineral acid are required for neutralization which is to be contrasted with the amounts required when NaOH, for example, is used for the extraction of resin acids.

Desirably, I may subject to selective solvent refining the resin acids recovered from the inal extract. Thus, I may treat with an immisible selective solvent for color bodies, such as furfural, phenol, etc., a solution of the recovered rosin acids either in the nal extract solution or redissolved in a suitable solvent such as light petroleum distillate. This stepl is particularly suitable where an unreflned rosin was originally taken.

By selective solvent refining the product in this way, I produce a product even lighter in color and still richer in resin acids and lower in neutral bodies.

The residual rosin or modied rosin .rich in neutral bodies may also be refined. If desired, its neutral body content may be decreased by distillation, alkaline extraction, etc.

The products produced by the present invention are new so far as I am aware. Thus, when the invention is applied to rosin such as ordinary woodrosin, the extracted rosin acids constitute an improved rosin which hasV great rfreedom from crystallizing tendencies, a drop merized wood rosin, an improved polymerized l rosin is obtained from the extract, having a drop if the extraction is very prolonged, the residuewill consist chiefly of neutral bodies and will be a soft liquid.

The product obtained by treatment of hydrogenated rosin in accordance with the invention is likewise thought to be new. Thus, from the extract from hydrogenated rosin I obtain a hydrogenated rosin having a drop melting point above 83 C., an acid number of from 170 to 180, and a content of unsaponiflable matter yless than 5%.

The new non-crystalline hydrogenated rosin product in accordance with this invention is also obtained 4by subjecting the extracted rosin product of drop melting point above about 87 C.,

acid number of about 175-180 and unsaponifiable content less than 5% to hydrogen and a hydrogenation catalyst under hydrogenation conditions of pressure, temperature and time effective to'bring about hydrogenation of rosin acids. For example, the rosin extract product in an inert solvent such as hexane is subjected to hydrogen at any convenient pressure, such as abouttwo atmospheres, at a non-decomposing temperature such as about 50 C., in the presence of a platinum or palladium hydrogenation catalyst. Nickel hydrogenation catalyst may be employed under hydrogenation conditions therefor with like results. The hydrogenation may be carried out at any lstage in the process, i. e., before or after extraction, in fused form or in solution atiany stage, although preferably hydrogenation is carried out in a non-aqueous phase. v l

'I'he hydrogenated rosin subjected to the alkali metal inorganic salt extraction process in accordance with this invention may also be a product obtained by first polymerizing rosin and then hydrogenating it. The extracted rosin product thereby obtained will be higher melting but otherwise similar to the extracted hydrogenated rosin product. Thus, the resulting extracted,

non-.crystalline and non-crystallizing, hydrodrop melting point above about 96 C., an acid number of from 170 to 180 and a. content of unsaponiiiable matter of less than 5%.

This product is also obtained ii an extracted polymerized rosin product prepared as herein disclosed is subjected to hydrogen in the presence of a hydrogenation catalyst under hydrogenation conditions. Thus, the hydrogenated rosin product according to this invention may be a polymerized rosin product and the process for its preparation comprises polymerizing rosin, extractng a solution of the polymerized rosin with the inorganic alkali metal salt aqueous solution of pH 8-12 followed by extracting therefrom with the immiscible Solvent, as hereinbefore described, and hydrogenating the acid content of the polymerized rosin product extracted at any stage following the polymerization step, i. e., before or after either or both extraction steps, and preferably while the polymerized rosin material is in a non-aqueous phase. Polymerization and hydrogenation steps may both follow the extraction steps and may each be applied at any stage, polymerization preceding hydrogenation.

The process is eiective in the removal of the polymerizing catalyst from polymerized rosin. Thus where sulfuric acid is present in crude polymerized rosinl application of the process of the present invention enables its ready separation from the polymerized rosin acids. furic acid and complexes thereof are so strong that they stay with the borax or other extracting salt and are nonextractable by the ether or 1 Two hundred and fty parts by weight FF wood rosin were dissolved in 700 parts by weight diethyl ether and extracted with 1000 parts by weight 5% borax (pH-9.0). The borax ex- The sul- First Second Third 4000 parts borax Fourth 4000 parts borax solution yielded tract was then extracted with 700 parts by weight4 First 4000 parts by weight borax solution yielded Second 4000 parts by weight borax solution yielded Third 4000 parts by weight borax solution yielded Fourth 4000 parts by weight borax solution yielded Filth 4000 parts by weight borax solution yielded Total borax extroctable acids 120.

The borax extractable acids were rened by washing a 20% solution in narrow range gasoline (B. R. 20D-270 F.) with 40 parts by weight furfural, then with 20 parts by weight furfural three times. Finally two washes with 15 parts moval of the solvent. graded M in color. A similar rening of the original FF rosin with all but the last furfural washes yielded a rosin grading K in color.

EampleZ Two hundred and fifty parts by weight of a polymerized rosin melting at 98-99" C. (drop method) and having an acid number 154.5-155.5 were dissolved in u parts by weightvof diethyl ether and extracted as in Example 1. The yield of resin acids was as follows:

First 4000 parts borax solution yielded 51.1 parts resin acid Second 4(00 parts borax solution yielded 30.0 parts resin acid 'ihird 4000 parts br-ax soution yielded 1.8 parts resin acid Fourth 4000 parts borax solution yielded 2.0 parts resin acid Total borax extractable acids 84. 9 parts by weight 'I'he melting point of the acids was 104.7 (drop method). The acid number was 177.0, the saponication number was 180.7 and the thiocyanogen number was 68.2.

Example 3 Two hundred and fifty parts by weight of a heat treated rosin in 350 parts by weight of diethyl ether were extracted with 500 parts by weight of 5% borax as in Example 1. The borax extracts were each washed with 350 parts by weight of diethyl ether to remove the resin acids. The yields of acids were as follows:

4000 parts borax solution yielded 09.6 parts by weight resin acid 4000 parts borax solution yielded 37.0 parts by weight resin acid solution yielded 16.6 parts by weight resin acid 1. 3 parts by weight resin acid Total 124. 5

The melting point of the acids was 87.7 C., the

acid number was 174.7, and the saponification Five hundred parts by weight I gum rosin (M. P. 86 C.) were dissolved in 350 parts by weight diethyl ether and extracted with 500 parts by '.Jeight of 5% borax solution. The borax extracts were each washed with 350 parts by weight of ether to remove the resin acids. The extraction was carried out as in Example 1,- 32 extractions being made. The resin acids were recovered by evaporation of the ether. The total amount of resin acids thus obtained amounted to 433 parts by weight. The melting point of the acids was 91 C. The ester gum of the acids melted at 101 C.

Example 5 Two hundred and tlf-ty parts by weight of wood rosin were dissolved in 870 parts by weight of toluene and the solution extracted with 1000 parts by weight oi 5% borax solution. The borax 8 parts by weight resin acids 5. 2 parts by weight resin acids l2. 5 parts by weight resin acids 2 parts by weight resin acids 6 parts by weight resin acids solution was then extracted with 870 parts by weight of toluene. The extraction with borax and extraction of the borax solution with toluene was repeated three times. From 4000 parts by weight of borax extract there was thus obtained furfural each were given. The rosin after re- 3.2 parts by weight of resin acid.

Example 8 Five hundred parte byweight 1" wood rosin were dissolved in 1250 parts by weight oi petro leum ether. 'This solution `was extracted with 2000 parts by weight 5% b0rax. The borax solution was.- then extracted with 1250 parts by weight o! petroleum ether. This extraction with borax and extraction ot the borax with petroleum ether was repeated again. From the petroleum ether there was obtained by evaporation 8.3 parts by weight of resin acid.

o Example 7 Two hundred and nity parts by weight 1" wood rcsin were dissolved in '100 parts by weight' of diethyl ether and extracted with 1000 parts by weight of 5% borax solution. The borax solution was then extracted with 700 parts diethyl ether to remove the resin acids. This process of extraction was repeated twenty-three times. The resin acids were isolated by evaporation of` th ether. The results were as follows: f

rim 4000 pm. weighs boi-sx yielded ses pme min ma Second 4000 parts iby weight borax yielded 71. 4 parts resin acid Third 4000 parts by weight borax yielded 11. 5 parts resin acid Fourth 4000 parte' by weight borax yielded 2. 0 parts resin acid Filth 4000 parts by weight borax yielded l. 9 parts resin acid Sixth 4000 parts by weight borax yielded 1.4 parts resin acid Total 17L 8 The melting point of me acids was 89.5 c.. the

acidnurnber was 176.9, the saponiijlcation numacid number of 174.0, `a saponiiicationnumber of 176.7, and a thiocyanogen number of 28.0. The ester gum of the acids melted above 90 C.

Example 9 A solution of 250 parts by weight of K wood rosin in 300 parts by weight diethyl ether was agitated with four portions 0f 5% NaaPO4J2HzO solution (pH 11.0) amounting to 500 parts by weight each. After complete separation into two layers, the trisodium phosphate layers were separated and each extracted with one portion oi' diethyl ether amounting to 300 parts by weight.l The resulting 1200 parts by weight of diethyl the treatment oi' Palkin et al. markedly increases l ether were evaporated to obtain the resin acids 5 which amounted to 9.0 parts by weight.

Example 10 A By substituting 3.4% sodium metaborate solu- Example 11 tion (pH 8.2) for the trisodium phosphate solution in Example 9 and carrying out the process as outlined in Example 9, the yield of resin acid from the 1200 parts `by weight of diethyl ether was 7.7 parts by weight.

i Example 13 By substituting' 3% Naicoazmo solution.'

(pH 10.7) tor the trisodium phosphate solution in Example 9 and carrying out two of the extraction processes outlined in Example 9, the yield of resin acid from 600 parts by weight of diethyl ether was 19.1 parts-by weight. o

Example 14 v Five hundred parts by weight crude pineoleoresin were dissolved by gentle heating with 250 parts by weight diethyl ether. The solution was filtered to remove water and foreign matter. The

filtrate was extracted with 500 parts by weight oi' 5% borax solution. The borax extract was washed with 350 parts by weight of ether to re' move the resin acids. 'I'he extractlonwas repeated as in Example 1, thirty-'two extractions being made. The resin acids were recovered byevaporation oi' the ether extracts.

Example 15 I Five hundred parts byweight of sc-called nonv crystallizing gum rosin (prepared by the method oi' Palkin et al., U. Si P. No. 2,176,660) were commingled with 350 parts by weight diethyl ether and the solution extracted withv 500 parts by the unsaponiilable content.

As used in this speciiication and in the claims appended hereto, the term modied rosin" refers to ordinary rosin which has been treated so as to chemically change its rosin nucleus without substantially aiifecting its carboxylic acid grouping, as for example by heat treatment, isomerization, hydrogenation, polymerization, disproportionation, etc. The term solvent capable of immiscibility" is used to include solvents which either are immlscible or may be made immlscible as by changing the temperature.

. This application is a continuation-impart or my copending application, Serial No. 381,779, tiled March 5, 1941.

It will be understood that the details and examples hereinbei'ore set 'forth are illustrative only and that vthe inventionas broadly described and claimed is in no way limited thereby.

What I claim and desire to protect by Letters y Patent ist 'By substituting 3% disedium phosphate solution (pH 9.0) for the `triso'dium phosphate solution in Example 9 and carrying r out the process as outlined in Example 9, the lyield of resin acid v Example. 12

1. The process of refining hydrogenated rosin products which comprises bringing into contact a solution oi' a resin selected from the group consisting oi hydrogenated rosin and hydrogenated polymerized rosin and an aqueous solution capable of immiscibility therewith of an inorganie alkaline salt of an alkali metal, the said solution having a pH between about 8 andy about l2, extracting acidic components from the initial resin solution into the alkaline salt solution; separating the salt solution from the resin solution.

By substituting' 3% sodium bicarbonate soiu- 75 bringing the salt solution into contact with a solvent capable of immiscibility therewith, the

said solvent being a solvent for resinacids but salt, the acid thereof, and the alkali salt-resin acid extraction product, extracting resin acids from the salt solution into the solvent immiscible therewith, and separating the resulting solvent phase containing extracted resin acids from the salt solution.

2. The process of refining hydrogenated rosin products which comprises bringing into contact a lower aliphatic ether solution of a resin selected from the groupconsisting of hydrogenated rosin and hydrogenated polymerized rosin and an aqueous solution capable of immiscibility therewith of an inorganic alkaline salt of -an alkali metal, the said solution having a pH between about 8 and about 12, extracting acidic components from the initial resin solution into the alkaline salt solution, separating the salt solution from the resin solution, bringing the salt solution into contact with a'lower aliphatic ether, ex-

tracting resin acids from the salt solution into the lower aliphatic ether, and separating the resulting ether phase containing extracted resin acids from the .salt solution.

3. The process of rening hydrogenated rosin products which comprises bringing into contact a solution of a resin selected from the group consisting of hydrogenated rosin and hydrogenated polymerized rosin and an aqueous solution capable of immiscibility therewith oi' a salt of a boric acid and an alkali metal, the said borate solution having a pH between about 8 and about 12, extracting acidic components from the initial resin solution into the borate salt solution, separating the borate salt solution from the resin solution, bringing the borate salt solution into contact with a solvent capable of immiscibility therewith, the said solvent being a solvent for resin acids but substantially non-solvent forthe alkali metal salt, the boric acid thereof, and the alkali metal borate-resin acid extraction product, extracting resin acids from the borate salt solution into the solvent immisible therecontaining extracted resin acids from the borate salt solution.

4. The process of rening hydrogenated rosin products which comprises bringing into contact nents from the initial resin solution into the borate salt solution, separating the borate salt solution from the resin solution, bringing the borate salt solution into contact with a lower aliphatic ether, extracting resin acids from the borate salt solution into the low'er aliphatic ether, separating the resulting ether phase containing extracted resin .acids Vfrom the borate salt solution, and further extracting resin ether solution with the ether extracted aqueous alkali metal borate solution.

6. The process of rening a hydrogenated polymerized rosin which comprises bringing into contact a solution-of said hydrogenated polymerized rosin and an aqueous solution capable of immiscibility therewith of an inorganic alkaline \`salt of an' alkali metal, the said solution havi ing the salt solution into contact with a solvent vwith, and separating the resulting solvent phase a lower aliphatic ether solution of a resin selected from the group consisting of hydrogenated rosin and hydrogenated polymerized rosin and an aqueous solution capable of immiscibility therewith of a salt of a boric acid and an alkali metal,

. the said solution having a pH between about 8 tion into the lower aliphatic ether, and separating the resulting ether phase containing extracted resin acids from the boratesalt solution.

5. The process of reilning hydrogenated rosin products which comprises bringing into contact -a lower aliphatic ether solution of a resin selected i'rom the group consisting of hydrogenated rosin and hydrogenated polymerized rosin and an aqueous solution capable of immiscibility therewith of a salt of a boric acid and an alkali metal, the said solution having a pH between about 8 and about 12, extracting acidic compocapable of immiscibility therewith, the said solvent being a solvent for resin acids but substantially non-solvent for the alkali metal salt, the

acid thereof, and the alkali salt-resin acid extraction product, extracting resin acids from the salt solution into the solvent immiscible therewith, and separating the resulting solvent phase containing extracted resin acids from the salt solution.

'7. The process of preparing a refined hydrogenated pclymerized rosin product which comprises polymerizing rosin, bringing into contact a solution of the resulting polymerized rosin and an aqueous solution capable of immiscibility therewith of an inorganic alkaline salt of an alkali metal, the said solution having apH between about 8 and about 12, extracting acidic components from the initial resin solution into the alkaline salt solution, separating the salt solution from the resin solution, bringing the salt solution into contact with a solvent capable of immiscibility therewith, the said solvent being a solvent for resin acids but substantially non-solvent for the alkali metal salt, the acid thereof, and the alkali salt-resin acid extraction product, extracting resin acids from the salt solution into the solvent immiscible therewith, separating the resulting solvent phase containing extracted resin acids from the salt solution, hydrogenating the resin acid content of the polymerized rosin product extracted at any stage following the said step of polymerizing the rosin, and recovering the retlned hydrogenated polymerized rosin product.

8. The process of rening a hydrogenated polymerized rosin product which comprises bringing into contact a solution of ahydrogenated polymerized rosin and an aqueous solution capable of immiscibility therewith of a salt -of a boric acid and analkali metal, the said borate solution having a pH between about 8 and about l2, extracting acidic components from the initial resin solution into the borate salt solution, separating the borate salt solution from the resin the said solution havinga pH .between about 8 and about 12, extracting acidic components from the hydrogenated polymerized rosin solution into the borate salt solution, separating the borate salt solution from the hydrogenated polymerized rosin solution, bringing the-borate salt solution into contact with a lower aliphatic ether. extracting hydrogenated polymeriz'ed lrosin acids from theborate salt solution into thelower aliphatic ether, separating-the resulting ether phase containing extracted hydrogenated polymerized rosin acids from the borate salt solution, and recover ing a hydrogenated polymerized rosin product of increased melting: point from the ether solution.

10. 'I'he process ofreiining hydrogenated rosin which comprises bringing into contact a solution oi thesaid hydrogenated rosin and an aqueous solution capable of immisclbility therewith oi an inorganic alkalinesalt of an alkali metal, the said solution having a pH between about 8 and about 12, extracting acidic components from the initial hydrogenated rosin solution into the alkaline salt solution, separating the salt solution iroxnthe hydrogenated rosin solution, bringing the salt solution into contactI with the solvent capable oi' immiscibility therewith.. the said solvent being a solvent ior hydrogenated rosin acids but substantially non-solvent for the alkali metal salt, the acid thereof, and the alkali salt-hydrogenated rosin acid extraction product, extracting hydrogenated rosin acids from the salt solution into the solvent immlscible therewith, and separating the resulting solvent phase containing extracted hydrogenated rosin acids from the salt solution.

11. The process of preparing a refined hydrosalt solution into contact with a lower aliphatic ether, extracting hydrogenated .rosin acids from the borate salt solution into the lower aliphatic ether, separating the resulting ether phase containing extracted hydrogenated rosin acids from the borate salt-solution, and recovering a hydrogenated rosin product of increased melting point from the ether solution. i

13. The process of refining hydrogenated rosin which comprises bringing into contact a solution oi the hydrogenated rosin in diethyl-'ether and an aqueous solution capable oi imxniscibility therewith ofva sodium salt of a boric acid having a concentration between about 0.5% and about 10% of the said sait and a pH between about 8 and about 12, extracting 'acidic components from .the hydrogenated rosin solution into the borate theiresulting ether phase containing extracted genated rosin which comprises forming a solution of rosin, bringing into contact the rosin solution and an aqueous solution capable of immiscibility therewith of an Ainorganic alkaline salt oi an alkali metal, the said solution having a pH between about 8 and about l2, extracting acidic components from the rosin solution into the alkaline salt solution. separating the salt solution from the rosin solution, bringing the salt solution into contact with a solvent capable oi' immiscibility therewith, the said solvent being a solvent for rosin acids present but substantially non-solvent for the alkali metal salt. the inorganic acid thereof, and the alkali metal saltrosin acid extraction product, extracting rosin acids from the salt solution into the solvent immiscible therewith, separating the resulting solvent phase containing extracted rosin acids from the salt solution, hydrogenati'ng the rosin acid content of the extracted product at any stage of the process, and recovering the rened hydrogenated rosin product.

12. The process oi' refining hydrogenated rosin which comprises bringing into contact a solution of the hydrogenated rosin and an aqueous solution capable of immiscibility therewith of a salt of a boric acid and an alkali metal, the said solution having a pH between about 8 and about 12, extracting a cidic components from the hydrogenated rosin solution into the borate salt solution, separating the borate salt solution trom the hydrogenated rosin solution, bringing the borate hydrogenated rosin acids from the 'borate salt vsolution and recovering a hydrogenated rosin product of increased melting point vfrom the ether solution. v'

14. The process of reiining hydrogenated rosin which comprises bringing into contact a lower aliphatic ether solution of 'the hydrogenated rosin and an aqueous solution lmmiscible therewith of a sodium tetraborate, the said solution having a pH between about 8 and about 12, extracting acidic components from the hydrogenated rosin solution into the borate salt solution, separating the borate salt solution from the hydrogenated rosin solution, bringing the borate'salt so lution into contact with a lower aliphatic ether extracting hydrogenated rosin acids from th borate saltsolution into the lower aliphatic ethei separating the resulting ether phase containin extracted hydrogenated rosin acids from th borate salt solution', and recovering a hydrogen ated rosin product of increased melting poin from the ether solution.

15. The process oi.' rening hydrogenated rosin which comprises bringing into contact a lower aliphatic ether solution of the hydrogenated rosin and an aqueous solution immiscible therewith of a sodium` metaborate, the said solution having a pH between about 8 and about 12, extracting acidic components from the hydrogenated rosin solution intovthe borate salt soultion, separating the borate salt solution from the hydrogenated rosin solution,A bringing the borate salt solution into contact with a lower aliphatic ether, ex-

. tracting hydrogenated rosin acids from the borate genated rosin product selected from the group consisting of non-crystalline mixtures of essentially hydrogenated rosin acids and non-crystalline mixtures of essentially hydrogenated poly- `merized rosin acids, said acids being derivable respectively from hydrogenated rosin and hydrogenated polymerized rosin, said hydrogenated rosin product having a drop melting point above 83 C., an acid oi from 17o-180. and a content of unsaponifiable matter less than 5%.

17. As a new article oi manufacture a hydrogenated rosin product consisting essentially of a non-crystalline mixture of hydrogenated rosin acids derivable from hydrogenated rosin, said hydrogenated rosin product having a drop melting point above A83 C., an acid number of from 17.0- 5

180, and a. content ofunsaponiabie matter less than 5%. n

18. As a new article .of manufacture a hydrosentiaily of a non-crystalline mixture of hydrogenated poiymerized rosin acids derivable from hydrogenated polymerized rosin.' said hydrogenated polymerized rosin product having a drop melting point above about 96 C., an acid number of from 110-180, and a content of unsaponiable matter less than 5% RICHARD F. B. COX.

Twentse. 2,529,516.

CERTIFICATE oF conREcTI'oN. l vseptember '1L,19u5. RICHARD F. B. cox.

It is hereby certified that error .appears in the printed specification of the above numbered patent', requiring' correction as follows: Pago3, first column, 1ie70','for 'immisib1e read ',--immiscible-w; page '7, second cgl- Y umn, line 55, claim 15,'forrsou1tiozo" read so1ution; line 75, claim 16, afte "scid," insert .-mmber--' pd tnagtne'ssmmtferg Patent; shoula 'be read 'with 4tio-is; confection. there'i lthat'tllie saine may conform-to the rec- 'o1-d `of the cs'e i the Potent Office. Y

Signed snd sealed' this 9th-defer ovemb'e-,I' 19143- Henry'van A'rsdale, (Seal) Acting Commissioner of Patents. 

